Resins from selected distillates



Stanley B. Mirviss; Roselle, N. J., assign'ors to Esso- Research and Engineering Company, a corporation of Delaware No Drawing. Application D ecember 22, 1952-,

Serial No. 327,438

5 claims. ((312 260-82) This invention is concerned with the preparation of light-colored, high softening pointresins from piperylene containing fractions boilingin theran'ge of 30' to 60 C. which are obtained as selected distillate cuts from steam cracked petroleum streams.

In general, heavier petroleum fractions such as naphtha, gas oil, and the like, are cracked at relatively low pressures and at temperatures of 1000 to 1500 F. in the presence of steam and for relatively short contact times. The gas and liquid streams produced contain large quantities of diolefins and olefins in the C5 to C10 range. The naphtha distillate streams obtained by steam cracking operations contain large amounts of diolefins, olefins, aromatics and some para'fiins.

In order to obtain the selected polymerization feed streams to be used in this invention, the distillate streams are processed to remove the cyclopentadienes and also the isoprene, if desired.

By using a thermal soaking ofthe C5 containing fraction at a temperature of 100 to 250 F. and suifieient heat treating time, the cyclodie'nes, mainly the cyclopentadienes, are dimerized and are separated by vacuumor steam distillation. Inthis distillation, the hydrocarbons boiling below the dimers are removed as an overhead distillate leaving the dimer-rich residual fraction.

It has now been found that the low-boiling components of this overhead distillate are particularly Well suited as feeds for the preparation of light-colored, high softening point resins. The fractions boiling from about 30 C. (the initial boiling point of the fraction) up to 60 are treated with an aluminum halide catalyst at 30 to +70 C. Even higher temperatures may be employed although operating at such temperatures requires pressure equipment. Light yellowish resins can thus be produced in a yield of at least 40% based on the hydro= carbon feed. These resin products have softening points in the range of 75 to 100 C. The volatile, unpolymerized components recovered from the polymerization step can be used as feed stock for oxonation reactions, if desired, to produce valuable aldehydes and alcohols; for hydration to alcohols and for alkylating aromatics.

The preferred feed stocks are fractions boiling from 30 to 60 C., and are relatively free of cycloperitadienes. It is particularly desirable that at least 40% of the polymerization feed comprises components boiling in the range of 38 to 46 C. Various cuts within 30 to 60 range can be used as long as the piperylene concentration of the cut is within acertain specified range, particularly about 15 to not more than about 60 volume per cent. The following table shows characteristic compositions of these distillate streams:

Component: Vol. per cent Isoprene 15-0 Piperylenes 15-60 C5 acyclic and cyclic olefins 70-35 Parafiins and naphthenes -3 Ce+ 0-2 nited States Patent 0 l 2,753,325 Patented July 3, 1956 Specific examples of. cuts which are satisfactory are shown below. One cut shown which contains 73% piperylene is unsatisfactory as resin feed.

FeedxNo;. 1- 2 i 3 4 5 i Distillation Range, C 30-60 30-48 35- 18 38-46 38-46 V01. Percent in 3846 0 Range 60 7'5 90 92 Feed (0 Vol. Percent Piperylene 15 20 38 54 73 Vol. Percent Isoprene 14 15 14 1 3. 5

3 Satisfactory. l Unsatisfactory.

Volume Percent Isoprene 1 3. 5 t-Piperylene 39 63 eis-Piperylene 15 10 Oyclopentene 15 9 5 0lefins 27 13 G5. Saturates 2 1 The reactive componentsin the stream are polymerized inthe presence of an aluminum halide catalyst. Aluminum chloride. and aluminum bromide can be used either in the solid or powderedformor as slurries in inert diluents. Solubilized aluminum halide catalysts are also quite satisfactory and are preferred. for giving the best gel-free products. Also, the aluminum halide may be addedin the form of a complex. If desired, the. complex maybe formedby interaction of A1Cl3 with. the. unreacted-hydrocarbons strippedfrom resin product or from naphth-as containing 'olefins and aromatics. As oneillusitrati-on a naphtha containing: about 60% olefinsand. 40% aromatics is satisfactory. Preferred catalyst concentra tions are in the range of 0.25 to 2.5 based on. the hydrocarbon feed. The reaction is carried out at temperaturesin the range of 30' to C., preferably -10 to +55 C. A diluent may be used if desired.

The polymerization reaction is carried out as a liquid phase operation. The catalyst may be added continually or batchwise. Any practical and effective methods for adding catalyst and reagents can be utilized. The time required to carry out the reaction depends primarily on the rate that the catalyst can be added that will allow adequatecontro'l of the reaction temperature. The reaction products are worked up by Water or caustic washing or by Washing with dilute H2804 (5%) followed by water washing; The catalyst residues can also be removed by precipitation as a methanol catalyst complex followed" by subsequent filtration. The latter process provides for removal of any insoluble polymer formed during the course of the polymerization. The polymerized reaction product is then stripped free of unreacted components of the feed and low molecular weight polymerization products to give the final resin.

The yield and softening point of the final resin will depend on the degree of stripping. Stripping to a pot temperature of 200-300 C. at 1-50 mm. Hg, preferably 240-270 C. at 1 to 5 mm. Hg has given acceptable resin product's. Steam stripping at temperatures of 250-270 C. can also be employed to produce high softening point resins.

The resins are compatible with and can be readily cobodied with non-conjugated drying oils at linseed, soya and the like. Although the bodying rate with highly conjugated oils as tung or oiticica is very rapid, the resins can be used satisfactorily with linseed-tung oil blends or soyaoiticica, etc. to give excellent varnishes. These varnishes can be prepared by cooking at temperatures as high as 550 F. without encountering insolubilization. Cooking losses are low, e. g. 6% or less. The varnishes are especially useful for can coating applications because of their excellent flexibility and chemical resistance characteristics. Baked films prepared from cobodied solid resins and a 50/50 linseed/tung mixture (20 lbs. resin/ 100 gallons of oil) show no failures upon bending (as in can forming operations). The resins are also suitable for use in printing ink formulations.

feeds having up to about 55-60% of piperylene (the remainder of the feed being largely olefinic) are satisfactory as resin feed streams, giving good yields of resins of high softening point, light color, and low iodine number with relatively small amounts of insoluble polymer. The olefinic feed having more than about 60% of piperylene gave a greatly decreased yield of soluble resin having a low softening point and large amounts of insoluble polymer. Details are shown in Table II below.

Table 11 Vol. percent Wt. percent Resin Properties Feed Boiling 1,8-Penta- Percent Range, 0. diene Catalyst (piperylene) Sol. Insol. Soft. Color Iodine in Feed Resin Polymer Pt., C. Number 30-48 20 1% A1013 49. 2 9. 8 77 235 30-480 20 1% AlCla* 57. 2 None 78 1 38-4fi 54 1% A1013 68. 3 2. 3 84 0 209 3846 54 1% A1013... 65.5 None 78 1 38-46"- 54 1% AlBra 65.0 2. 0 84 0 215 38-46 73 0.7% AlCl 35. 8 22 25 1 255 *Added as a soluble liquid hydrocarbon complex.

Complex prepared by adding solid A101; to a mixture of C-C8 olefins (60%), benzene (30%) and toluene The invention will be described in greater detail by the following examples:

EXAMPLE 1 EXAMPLE 3 A steam cracked distillate stream boiling from 3846 C. and containing 54% piperylene and about 42% C5 olefins was polymerized with AlCla at temperatures varying from l0 to C. The resin products were of uniformly good quality. The data of the experiments are shown in Table III.

Table III eration was fractionated to obtain a cut boiling in the" 35 Yield Wt Percent Be who range of about 30 to C. This cut contained about Reaction s p Wt. Percent T 15% 1,3-pentad1cne (piperylene). Samples of the d1s Catalyst 3 6! S01 Insol Soft Iodine tiulate fraction were then treated with AlCls or with BFs Resin polym'er Pt" 0 {3. Color Number at reaction temperatures 1n the range of 0 up to about 25 C. The reaction products were then water washed 20 617 25 77 0 220 or treated with CHsOH to remove residual catalyst, fili8 23-; g: g 38% tered and then stripped to a bottoms (resin) temperature 20 1 84 o 2 of 270 C. at 3-4 mm. Hg. Specific data are shown in 35 84 0 221 Table I below:

5 Table 1 Catalyst Yield, Wt. Percent Resin Properties Reaction Temp, Amount, C. Soluble Insoluble Soft. Iodine Int. Type Percent Resin Product CPS, Color No. Vrsc.

0 67 s10 61. 2 4. s 76 0 238 .058 0 66 10-15 56.3 6.2 79 1 192 1 0 10-15 49. 2 6.8 88 0 235 066 0 61 15-20 43.3 3. 2 s2 1 184 1 0 15-20 48.4 5.5 79 0 225 .058 0 3 41.5 25 1 0 67 15-20 48.5 25 0 250 .029

1 Ring and ball method (ASIM E-28-5l-T). 1 Color of solution of 1 g. resin in 67 ml. xylenes compared to Gardner color index. 3 ASTM (D-555-47).

The comparative data shown above indicate the great EXAMPLE 4 advantages obtained in preparing resins by this invention. The soluble resin is produced in good yield with relatively small amounts of insoluble gelled product. The AlCls catayst produced a resin having a softening point well above 75 C., and a very light color. The BFs resin, however, has a softening point of less than 25 C. and a somewhat higher unsaturation (as indicated by the iodene number).

EXAMPLE 2 A series of experiments similar to that described in Example l was carried out. The distillate feed stream was varied somewhat, the percentage of piperylene varying from. 20 to 73%. These comparative experiments show 75 Table IV.

In another series of polymerizations, a fraction of steam These data show that solution of aluminum catalysts can be used to give high yields of excellent quality and completely soluble resins.

EXAMPLE 5 The steam cracked distillate fraction described in EX- ample 4 above was diluted with n-heptane to give a solution containing 62.5% of the unsaturated fraction. This solution was polymerized at 55 C. using 1% AlBra. The catalyst was added as a 6% solution in n-heptane over a period of /2 hour and the reaction mixture was held at 55 C. for an additional /2 hour with agitation. The reaction mixture was then quenched by the addition of 75 ml. of 5% H2SO4, water washed and then stripped to a bottoms (resin) temperature of 280 C. at 5 mm. Hg. The completely soluble resin product had a Gardner color of A2, a softening point of 98 C., and represented a yield of 69.2 wt. percent on the distillate portion of the polymerization feed.

What is claimed is:

l. A process for the preparation of soluble hydrocarbon resins having Gardner colors of about -1 which comprises subjecting a C fraction from a steam cracked petroleum stream containing about -60 volume percent piperylene and about 35-70 volume percent olefins to thermal soaking at a temperature of about 37 to 122 C. for a sufficient time to dimerize the cyclodienes, separating the fraction boiling between about 30 and 60 C. from the dimers, subjecting the undimerized portion to polymerization in the presence of aluminum halide catalyst until a yield of at least about 43 wt. percent soluble resins are obtained, and recovering the resins formed in the absence of alkalies.

2. A process according to claim 1 in which the undimerized portion is fractionated into a fraction boiling between 38 and 46 C. and is subjected to polymerization with aluminum chloride at a temperature between 10 and C.

3. A process according to claim 2 in which the fraction boiling between 30 and C. is subjected to polymerization in the presence of 0.25 and 2.5% of aluminum chloride the polymerization being continued until a yield of above about 60 wt. percent soluble resin having a Gardner color of about 0-1 is obtained.

4. A process according to claim 1 in which at least 40 per cent of the 30 to 60 C. fraction boils in the range of 38 to 46 C., which 40 per cent contains from 15 to 55 volume per cent of piperylene.

5. A process according to claim 1 in which the undimerized portion is separated into a fraction boiling from 48 to 36 C. having from 48 to 54 volume per cent of piperylene and is subjected to polymerization in the was ence of a solubilized aluminum halide catalyst at a temperature between -10 and +55 C. until a yield of at least about wt. percent soluble resin is obtained.

References Cited in the file of this patent UNITED STATES PATENTS 1,982,708 Thomas et al. Dec. 4, 1934 2,062,845 Thomas et al. Dec. 1, 1936 2,271,636 Frolich Feb. 3, 1942 2,521,022 Rowland Sept. 5, 1950 

1. A PROCESS FOR THE PREPARATION OF SOLUBLE HYDROCARBON RESINS HAVING GARDNER COLORS OF ABOUT 0-1 WHICH COMPRISES SUBJECTING C5 FRACTION FROM A STEAM CRACKED PETROLEUM STREAM CONTAINING ABOUT 15-60 VOLUME PERCENT PIPERYLENE AND ABOUT 35-70 VOLUME PERCENT OLEFINS TO THERMAL SOAKING AT A TEMPERATURE OF ABOUT 37* TO 122* C. FOR A SUFFICIENT TIME TO DIMERIZE THE CYCLODIENES, SEPARATING THE FRACTION BOILING BETWEEN ABOUT 30 AND 60* C. FROM THE DIMERS, SUBJECTING THE UNDIMERIZED PORTION TO POLYMERIZATION IN THE PRESENCE OF ALUMINUM HALIDE CATALYST UNTIL A YIELD OF AT LEAST ABOUT 43 WT. PERCENT SOLUBLE RESINS ARE OBTAINED, AND RECOVERING THE RESINS FORMED IN THE ABSENCE OF ALKALIES. 